System and Process for Making Formic Acid

ABSTRACT

Methods and systems for electrochemical production of formic acid are disclosed. A method may include, but is not limited to, steps (A) to (D). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte and a cathode. The cathode is selected from the group consisting of indium, lead, tin, cadmium, and bismuth. The second compartment may include a pH of between approximately 4 and 7. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient to reduce the carbon dioxide to formic acid. Step (D) may maintain a concentration of formic acid in the second compartment at or below approximately 500 ppm.

CROSS-REFERENCE TO RELATED APPLICATIONS

Noon The present application claims the benefit under 35 U.S.C. §119(e) of U.S. patent application Ser. No. 61/450,704, filed Mar. 9, 2011.

The above-listed application is hereby incorporated by reference in its entirety.

FIELD

The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical production of formic acid from carbon dioxide.

BACKGROUND

The combustion of fossil fuels in activities such as electricity generation, transportation, and manufacturing produces billions of tons of carbon dioxide annually. Research since the 1970s indicates increasing concentrations of carbon dioxide in the atmosphere may be responsible for altering the Earth's climate, changing the pH of the ocean and other potentially damaging effects. Countries around the world, including the United States, are seeking ways to mitigate emissions of carbon dioxide.

A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.

SUMMARY OF THE PREFERRED EMBODIMENTS

The present invention is directed to using metal cathodes and a controlled electrolytic solution to reduce carbon dioxide to various carbon moieties, preferably including formic acid. The electrolytic solution is preferably controlled by one or more of regulating its pH, selectively choosing a buffering system, regulating its temperature, and regulating the concentration of the carbon moieties. The present invention includes the process, system, and various components thereof.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not necessarily restrictive of the disclosure as claimed. The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate an embodiment of the disclosure and together with the general description, serve to explain the principles of the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The numerous advantages of the present disclosure may be better understood by those skilled in the art by reference to the accompanying figures in which:

FIG. 1 is a block diagram of a preferred system in accordance with an embodiment of the present disclosure;

FIG. 2 displays a table including preferred electrolytes used in electrochemical reactions of carbon dioxide and water to produce formic acid with an indium cathode;

FIG. 3 displays a chart of reactivity for hydrogen ions, carbon dioxide, and water species at the surface of the cathode from lower to higher pH ranges;

FIG. 4 displays a table of results of continuous removal of formic acid from an electrochemical cell according to one embodiment;

FIG. 5 displays a table of pH values and formic acid concentrations for production of formic acid from carbon dioxide and water with an electrochemical system using an indium cathode;

FIG. 6 is a flow diagram of a preferred method of electrochemical production of formic acid; and

FIG. 7 is a flow diagram of another preferred method of electrochemical production of formic acid.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Reference will now be made in detail to the presently preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings.

In accordance with some embodiments of the present disclosure, an electrochemical system is provided that generally allows carbon dioxide and water to be converted to formic acid. The present disclosure provides methods and/or systems for formic acid production with high efficiency and high stability preferably using an indium cathode in a system with appropriate electrolytes and pH range. Further, embodiments disclosed herein may employ a particular pH range without the use of a catalyst, and another pH range with use of a heterocyclic catalyst. Use of a heterocyclic catalyst may facilitate providing products including formic acid and other higher carbon-containing products.

The process of the present invention preferably produces formic acid electrochemically according to the following formula:

CO₂+H₂O→HCOOH+1/2 O₂

Embodiments are provided herein which describe use of a metal cathode, preferably indium, under appropriate process and cell conditions.

Before any embodiments of the invention are explained in detail, it is to be understood that the embodiments may not be limited in application per the details of the structure or the function as set forth in the following descriptions or illustrated in the figures. Different embodiments may be capable of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of terms such as “including,” “comprising,” or “having” and variations thereof herein are generally meant to encompass the item listed thereafter and equivalents thereof as well as additional items. Further, unless otherwise noted, technical terms may be used according to conventional usage.

In certain preferred embodiments, the reduction of the carbon dioxide to produce formic acid may be suitably achieved efficiently in a divided electrochemical or photoelectrochemical cell in which (i) a compartment contains an anode suitable to oxidize water, and (ii) another compartment contains a working cathode electrode, and in some embodiments, a catalyst. The compartments may be separated by a porous glass frit, microporous separator, ion exchange membrane, or other ion conducting bridge. Both compartments generally contain an aqueous solution of an electrolyte. Carbon dioxide gas may be continuously bubbled through the cathodic electrolyte solution to saturate the solution or the solution may be pre-saturated with carbon dioxide.

Referring to FIG. 1, a block diagram of a system 100 is shown in accordance with an embodiment of the present invention. System 100 may be utilized for electrochemical production of formic acid from carbon dioxide and water. The system (or apparatus) 100 generally comprises a cell (or container) 102, a liquid source 104 (preferably a water source), an energy source 106, a gas treatment/pressurization unit 108, a product extractor 110 and an oxygen extractor 112. A product or product mixture may be output from the product extractor 110 after extraction. An output gas containing oxygen may be output from the oxygen extractor 112 after extraction.

The cell 102 may be implemented as a divided cell. The divided cell may be a divided electrochemical cell and/or a divided photochemical cell. The cell 102 is generally operational to reduce carbon dioxide (CO₂) into formic acid. The reduction generally takes place by introducing (e.g., bubbling) carbon dioxide into an aqueous solution of an electrolyte in the cell 102. A cathode 120 in the cell 102 may reduce the carbon dioxide into a formic acid (and potentially other products). For instance, other products may include hydrogen, carbon monoxide, methanol and multi-carbon products such as acetone and isopropanol.

The cell 102 generally comprises two or more compartments (or chambers) 114 a-114 b, a separator (or membrane) 116, an anode 118, and a cathode 120. The anode 118 may be disposed in a given compartment (e.g., 114 a). The cathode 120 may be disposed in another compartment (e.g., 114 b) on an opposite side of the separator 116 as the anode 118. In a preferred implementation, the cathode 120 is an indium cathode, although other cathode materials may be suitable, including, without limitation, lead, bismuth, tin, and cadmium, provided the material facilitates the reduction of carbon dioxide to formic acid. An aqueous or preferably protic solution 122 (e.g., anolyte or catholyte 122) may fill both compartments 114 a-114 b. The aqueous solution 122 preferably includes water as a solvent and water soluble salts for providing various cations and anions in solution. Such anions may include, for example, sulfate (SO₄ ²⁻), perchlorate (ClO₄ ⁻), and chloride (Cl⁻). The catholyte 122 may include potassium sulfate, potassium chloride, sodium chloride, sodium sulfate, lithium sulfate, sodium perchlorate, and/or lithium chloride. A table 200 of exemplary electrolytes 202 used in electrochemical reactions of carbon dioxide and water to produce formic acid with an indium cathode is shown in FIG. 2. The table 200 also includes an indication of a pH 204, a potential (in volts vs. SCE (saturated calomel electrode)) 206, a FY (faradaic yield) 208, and a range of faradaic yields 210 for each electrolyte 202. Faradaic yield refers to the efficiency of electron transfer (as a percentage of total electrons transferred) for generation of a product, preferably formic acid in the present invention. Faradaic yield may be determined based on the formula: moles of product=Q/nF, where Q is the charge, n is the number of moles of electrons, and F is the Faraday constant (approximately 96485 C/mole).

In particular embodiments, a heterocyclic catalyst 124 may be added to the compartment 114 b containing the cathode 120, although in other embodiments, no heterocyclic catalyst 124 may be present. The heterocyclic catalyst 124 may include, for example, 4-hydroxy pyridine. The heterocyclic catalyst 124 may include one or more of adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, benzimidazole, a bipyridine, furan, an imidazole, an imidazole related species with at least one five-member ring, an indole, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole. When no heterocyclic catalyst 124 is utilized, formic acid is primarily produced by the cell 102. Use of the heterocyclic catalyst may enable the formation of products other than formic acid. It is believed that when a heterocyclic catalyst is used, the only products produced in significant amounts are formic acid, methanol, acetone, and isopropanol.

The pH of the compartment 114 b is preferably maintained between approximately 4 and 7 when no heterocyclic catalyst 124 is present. This pH range may be suitable to provide long-term stability of the cathode. In even more preferred implementations, the pH range is maintained between approximately 4.3 and 5.5 to provide concentrations of hydrogen ions (H⁺), carbon dioxide, and water at the surface of the cathode 120 that favor kinetics of carbon dioxide reduction at the cathode 120. The surface concentration of hydrogen ions, carbon dioxide, and water at the cathode 120 may play a role in the reduction of carbon dioxide or in another reaction, depending on the pH. FIG. 3 displays a chart of an approximated reactivity for hydrogen ions, carbon dioxide, and water species at the surface of the cathode 120 from lower to higher pH ranges. At low pH (e.g., less than about 4), the kinetics at the surface of the cathode 120 favor the reduction of hydrogen ions to hydrogen (H₂), whereas at a higher pH (e.g., greater than about 7), the kinetics favor the reduction of water to hydroxide species, which may cause the surface of the cathode 120 to become basic, thereby decreasing the kinetics of carbon dioxide reduction. At a moderate pH range (e.g., between about 4 and 7, and in particular, between about 4.3 and 5.5), the surface of the cathode 120 may favor the reduction of carbon dioxide, since a favorable distribution of hydrogen ions, water, and carbon dioxide species are present at the surface. In a preferred embodiment, the ratio of carbon dioxide to hydrogen ions and water at the surface of the cathode 120 generally includes about 5% to 60% carbon dioxide with about 40% to 95% hydrogen ions and water, and more preferably the ratio is 1:2 (e.g., about 33.3% carbon dioxide and about 66.6% hydrogen ions and water). When the heterocyclic catalyst 124 is present and an indium cathode is used, the pH of the cathode compartment 114 b is preferably below 5.5.

The liquid source 104 preferably includes a water source, such that the liquid source 104 may be operational to provide pure water to the cell 102.

The energy source 106 may include a variable voltage source. The energy source 106 may be operational to generate an electrical potential between the anode 118 and the cathode 120. The electrical potential may be a DC voltage. In preferred embodiments, the applied electrical potential is generally at or about −1.46 V vs. SCE, preferably from about −1.42 V vs. SCE to about −1.60 V vs. SCE, and more preferably from about −1.42 V vs. SCE to about −1.46 V vs. SCE.

The gas treatment/pressurization unit 108 preferably includes a carbon dioxide source, such that the gas treatment/pressurization unit 108 may be operational to provide carbon dioxide to the cell 102. In some embodiments, the carbon dioxide is bubbled directly into the compartment 114 b containing the cathode 120. For instance, the compartment 114 b may include a carbon dioxide input, such as a port 126 a configured to be coupled between the carbon dioxide source and the cathode 120.

Advantageously, the carbon dioxide may be obtained from any source (e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself). Most suitably, the carbon dioxide may be obtained from concentrated point sources of generation prior to being released into the atmosphere. For example, high concentration carbon dioxide sources may frequently accompany natural gas in amounts of 5% to 50%, exist in flue gases of fossil fuel (e.g., coal, natural gas, oil, etc.) burning power plants, and high purity carbon dioxide may be exhausted from cement factories, from fermenters used for industrial fermentation of ethanol, and from the manufacture of fertilizers and refined oil products. Certain geothermal steams may also contain significant amounts of carbon dioxide. The carbon dioxide emissions from varied industries, including geothermal wells, may be captured on-site. Thus, the capture and use of existing atmospheric carbon dioxide in accordance with some embodiments of the present invention generally allow the carbon dioxide to be a renewable and unlimited source of carbon.

The product extractor 110 may include an organic product and/or inorganic product extractor. The product extractor 110 is generally operational to extract (separate) one or more products (e.g., formic acid) from the electrolyte 122. The extracted products may be presented through a port 126 b of the system 100 for subsequent storage and/or consumption by other devices and/or processes. For instance, in particular implementations, formic acid is continuously removed from the cell 102, where cell 102 operates on a continuous basis, such as through a continuous flow-single pass reactor where fresh catholyte and carbon dioxide is fed continuously as the input, and where the output from the reactor is continuously removed. In other preferred implementations, the formic acid is continuously removed from the catholyte 122 via one or more of adsorbing the formic acid to a solid sorbent, liquid-liquid extraction, electrodialysis, and feeding the formic acid to bacteria that convert it to a secondary product. Removal of the product on a continuous basis may serve to prevent decreases in stability of an indium cathode, which may experience decreased stability at particular organic product concentrations. In a preferred implementation, the concentration of formic acid within the compartment 114 b is maintained at or below approximately 500 ppm, particularly when the applied voltage is −1.46 V vs SCE. In another preferred implementation, the concentration of formic acid within the compartment 114 b is maintained at or below approximately 300 ppm, particularly when the applied voltage is −1.46 V vs SCE. The concentration of formic acid may be detected via any suitable method, such as, for example, using ion chromatography (IC) to detect anionic species present in the aqueous solution and/or using Nuclear Magnetic Resonance (NMR) spectroscopy with a water suppression technique. Samples of the product of the cell 102 may be taken via an automated system for detection of the concentration of formic acid.

An example of results of continuous removal of formic acid from the cell 102 as the product is produced can be seen in table 400 of FIG. 4. Table 400 presents faradaic yields 404 over time (in hours) 402 of formic acid observed in electrochemical reactions of carbon dioxide and water with an indium cathode and a 0.5 M potassium sulfate (K₂SO₄) electrolyte with a potential of −1.46 V vs SCE. Formic acid concentrations were maintained between approximately 8 and 15 ppm for about 28 hours by continuously removing formic acid product from the compartment 114 b.

Other methods for ameliorating stability issues with cathodes at relatively high product concentrations include: adding more electrolyte to the compartment 114 b, adding divalent cations (preferably magnesium ions (Mg²⁺), barium ions (Bar), strontium ions (Sr2⁺), and/or calcium ions (Ca2⁺)) to the compartment 114 b (generally between about 0.001 mM to about 100 mM, preferably between about 1 mM to about 30 mM, and in a preferred embodiment the concentration of the divalent cations is about 2.65 mM (about 100 ppm)), increasing the temperature of the electrolyte 122, and/or increasing the pH of the compartment 114 b. An example of results of increasing the pH can be seen in table 500 of FIG. 5, where formic acid was produced from carbon dioxide and water with electrochemical system is using an indium cathode. Table 500 presents faradaic yields 508 over varying pH levels 504, various electrolyte compositions 502, and potentials (in volts vs. SCE) 506, where some electrolyte compositions 502 include 500 ppm of formic acid. As can be seen from table 500, while the observed faradaic yield 508 at a given pH level 504 decreased for every instance of including 500 ppm of formic acid as compared to when the 500 ppm of formic acid was not present, the decrease was less substantial at higher pH levels 504 (e.g., at pH of 6.6—with a decrease of approximately 17% with the 500 ppm of formic acid as compared to no added formic acid) than at lower pH levels 504 (e.g., at pH of 4.8—with a decrease of approximately 50% with the 500 ppm of formic acid as compared to no added formic acid).

The oxygen extractor 112 is generally operational to extract oxygen (e.g., O₂) byproducts created by the reduction of the carbon dioxide and/or the oxidation of water. In preferred embodiments, the oxygen extractor 112 is a disengager/flash tank. The extracted oxygen may be presented through a port 128 of the system 100 for subsequent storage and/or consumption by other devices and/or processes. Chlorine and/or oxidatively evolved chemicals may also be byproducts in some configurations, such as in an embodiment of processes other than oxygen evolution occurring at the anode 118. Such processes may include chlorine evolution, oxidation of organics to other saleable products, waste water cleanup, and corrosion of a sacrificial anode. Any other excess gases (e.g., hydrogen) created by the reduction of the carbon dioxide and water may be vented from the cell 102 via a port 130.

Referring to FIG. 6, a flow diagram of a preferred method 600 for electrochemical production of at least formic acid from carbon dioxide and water in is shown. The method (or process) 600 generally comprises a step (or block) 602, a step (or block) 604, a step (or block) 606, and a step (or block) 608. The method 600 may be implemented using the system 100.

In the step 602, water may be introduced to a first compartment of an electrochemical cell. The first compartment may include an anode. Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 604. The second compartment may include a solution of an electrolyte, a cathode selected from the group consisting of indium, lead, tin, cadmium, and bismuth, and a pH of between approximately 4 and 7. In the step 606, an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient to reduce the carbon dioxide to formic acid. Maintaining a concentration of formic acid in the second compartment below approximately 500 ppm may be performed in the step 608.

Referring to FIG. 7, a flow diagram of another preferred method 700 for electrochemical production of at least formic acid from carbon dioxide and water in is shown. The method (or process) 700 generally comprises a step (or block) 702, a step (or block) 704, a step (or block) 706, and a step (or block) 708. The method 700 may be implemented using the system 100.

In the step 702, a liquid may be introduced to a first compartment of an electrochemical cell. The first compartment may include an anode. Introducing carbon dioxide to a second compartment of the electrochemical cell may be performed in the step 704. The second compartment may include a solution of an electrolyte and a cathode. The electrolyte in the second compartment may have a pH which provides a concentration of hydrogen ions, carbon dioxide, and water at a surface of the cathode to favor reduction of carbon dioxide at the cathode. In the step 706, an electric potential may be applied between the anode and the cathode in the electrochemical cell sufficient to reduce the carbon dioxide to at least formic acid. Maintaining a concentration of formic acid in the second compartment below approximately 500 ppm may be performed in the step 708.

It is believed that the present disclosure and many of its attendant advantages will be understood by the foregoing description, and it will be apparent that various changes may be made in the form, construction and arrangement of the components thereof without departing from the scope and spirit of the disclosure or without sacrificing all of its material advantages. The form herein before described being merely an explanatory embodiment thereof, it is the intention of the following claims to encompass and include such changes. 

1.-10. (canceled)
 11. A system for electrochemical production of at least formic acid, comprising: an electrochemical cell including: a cathode; and a catholyte, the pH of the catholyte being maintained from 4.3 to 5.5, the catholyte including formic acid maintained at a concentration of no greater than about 500 ppm.
 12. The system of claim 11, wherein the electrolyte includes at least one of potassium sulfate, potassium chloride, sodium chloride, sodium sulfate, lithium sulfate, sodium perchlorate, or lithium chloride.
 13. The system of claim 11, wherein the second cell compartment includes a heterocyclic aromatic amine selected from the group consisting of 4-hydroxy pyridine, adenine, a heterocyclic amine containing sulfur, a heterocyclic amine containing oxygen, an azole, benzimidazole, a bipyridine, furan, an imidazole, an imidazole related species with at least one five-member ring, an indole, methylimidazole, an oxazole, phenanthroline, pterin, pteridine, a pyridine, a pyridine related species with at least one six-member ring, pyrrole, quinoline, or a thiazole, and mixtures thereof.
 14. The system of claim 13, wherein the heterocyclic aromatic amine is 4-hydroxy pyridine.
 15. The system of claim 13, wherein a multi-carbon containing product is produced in the cell.
 16. The system of claim 11, wherein the cathode is selected from the group consisting of indium, lead, tin, cadmium, and bismuth.
 17. The system of claim 16, wherein the cathode comprises indium.
 18. The system of claim 11, further including: an extractor configured for extraction of formic acid from the second cell compartment to maintain the concentration of formic acid to no greater than about 500 ppm.
 19. A method for electrochemical production of at least formic acid, comprising: (A) introducing a liquid to a first compartment of an electrochemical cell, the first compartment including an anode; (B) introducing carbon dioxide to a second compartment of the electrochemical cell, the second compartment including a solution of an electrolyte and a cathode, the electrolyte in the second compartment having a pH which provides a concentration of hydrogen ions, carbon dioxide, and water at a surface of the cathode to favor reduction of carbon dioxide at the cathode; (C) applying an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to at least formic acid; and (D) maintaining a concentration of formic acid in the second compartment at or below approximately 500 ppm.
 20. The method of claim 19, wherein the cathode includes at least one of indium, lead, tin, cadmium, bismuth, or indium.
 21. The method of claim 20, wherein the cathode comprises indium.
 22. The method of claim 19, wherein the liquid is water.
 23. A process for reducing carbon dioxide, the process comprising: (A) providing an electrochemical cell have a catholyte; (B) applying a voltage to the cell; and (C) monitoring the pH of the catholyte and the concentration of formic acid in the catholyte to generate a faradaic yield of at least 50%.
 24. The process of claim 22, wherein the cell includes an indium cathode.
 25. The process of claim 22, wherein the cell includes divalent ions.
 26. The process of claim 22, wherein the faradic yield is at least 60%.
 27. The process of claim 22, wherein the faradic yield is at least 70%.
 28. The process of claim 22, wherein the faradic yield is at least 80%.
 29. The process of claim 22, wherein the pH of the catholyte is maintained between about 4.3 and about 5.5.
 30. The process of claim 26, wherein the applied voltage is about −1.46 V vs. SCE. 